Porous silicon prepared with anodic currents of 5 to 30 mA/cm2 are characterized for structural and electronic properties of surface using photoluminescence, grazing angle X-ray diffraction, photoconductivity, thermally stimulated exo electron emission and work function measurements. The observed results indicate that with increasing porosity the crystallite size decreases and the amount of silicon hydride and oxide-type species increases, exhibiting a tendency similar to that of hydrogenated amorphous silicon and hydrogenated microcrystalline silicon. Free-standing powder of porous silicon, characterized by bright photoluminescence at 730 nm, showed crystallites of nanometre dimensions under the transmission electron microscope.